Method of bonding a window to a substrate using a silane functional adhesive composition

ABSTRACT

The invention is an adhesive composition comprising 
     a) i) a trialkoxysilane functional polyether or polyurethane wherein the polyether or polyurethane has a weight average molecular weight of 6000 or greater and a dialkyltin carboxylate or dialkyltin alcoholate; or 
     ii) a dialkoxysilane functional polyether or polyurethane and a dialkyltin alcoholate; and 
     b) a primary or secondary amino straight chain alkyl trialkoxysilane; 
     wherein the dialkyltin carboxylate or dialkyltin alcoholate is present in an effective amount to facilitate bonding of the adhesive to a substrate of from about 0.1 to about 1.0 percent by weight based on the weight of the adhesive and the primary or secondary amino straight chained alkyl trialkoxysilane is present in an amount which is effective to facilitate bonding of the adhesive to a substrate wherein the amount is from about 0.5 to about 1.2 percent by weight.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of application Ser. No.09/300,340 filed Apr. 27, 1999 now abandoned (incorporated herein byreference). This application claims the benefit of U.S. ProvisionalApplication No. 60/083,125 filed on Apr. 27, 1998 (incorporated hereinreference).

BACKGROUND OF THE INVENTION

This invention relates to an adhesive composition useful for bondingglass to a substrate and a method of bonding a window to a substrateusing a silane functional adhesive composition which is capable of beingused without the need for a primer.

Polyurethane sealant compositions typically are used for bondingnon-porous substrates, such as glass, to nonporous substrates, these aredescribed in U.S. Pat. No. 4,374,237 and U.S. Pat. No. 4,687,533, bothincorporated herein by reference. U.S. Pat. No. 4,374,237 describes apolyurethane sealant containing urethane prepolymers which have beenfurther reacted with secondary amine compounds containing two silanegroups. U.S. Pat. No. 4,687,533 describes a polyurethane sealantcontaining urethane prepolymers which contain silane groups which havebeen prepared by reacting a polyisocyanate having at least threeisocyanate groups with less than an equivalent amount of an alkoxysilanehaving a terminal group containing active hydrogen atoms reactive withisocyanate groups to form an isocyanatosilane having at least twounreacted isocyanate groups. In a second step, the isocyanatosilane ismixed with additional polyisocyanate and the mixture is reacted with apolyol to form a polyurethane prepolymer having terminal isocyanatogroups and pendant alkoxysilane groups. EP 856,569 discloses the use ofpolyoxyalkylene polymer terminated with silanes having hydrolyzablegroups bonded thereto blended with apolyoxyalkylene polymer having nocross-linking groups can be used for to bond glass to metal. Thisadhesives have not been a commercial success.

However, when such sealants are used to bond glass substrates to paintedsubstrates, such as for window installation in vehicle manufacturing,the lap shear strength of the bonded substrate may be less thandesirable for safety or structural purposes. Consequently, a separatepaint primer comprising a solution of one or more silanes is typicallyapplied to a painted substrate prior to the application of the sealantin most vehicle assembly operations for bonding the windshield and therear window. Further a separate primer is also applied to the ceramicfrit coated on the edge of the window (glass primer). The use of primersin assembly operations is undesirable in that it introduces extra steps,additional cost, the risk of marring the paint surface if dripped on anundesired location and exposes the assembly line operators to additionalchemicals. It would be desirable to provide a sealant which, when bondedto a painted substrate and glass then cured, provides a bond with ahigher lap shear strength, particularly when used in the absence of apaint primer and/or a glass primer.

SUMMARY OF THE INVENTION

The invention is an adhesive composition comprising

a) i) a trialkoxysilane functional polyether or polyurethane wherein thepolyether or polyurethane has a weight average molecular weight of 6000or greater and a dialkyltin carboxylate or dialkyltin alcoholate; or

ii) a dialkoxysilane functional polyether or polyurethane and adialkyltin alcoholate; and

b) a primary or secondary amino straight chain alkyl trialkoxysilane;

wherein the dialkyltin carboxylate or dialkyltin alcoholate is presentin an effective amount to facilitate bonding of the adhesive to asubstrate of from about 0.1 to about 1.0 percent by weight based on theweight of the adhesive and the primary or secondary amino straightchained alkyl trialkoxysilane is present in an amount which is effectiveto facilitate bonding of the adhesive to a substrate wherein the amountis from about 0.5 to about 1.5 percent by weight.

In another embodiment, the invention is a method of bonding a window ina vehicle. The process comprises applying to a window or a window frameof a structure an adhesive according to the invention; contacting thewindow with the window frame of a substrate wherein the adhesive islocated between the window and the substrate; and allowing the adhesiveto cure. This process is especially useful when the substrate isunprimed metal, plastic, fiberglass or a composite, optionally coatedwith a coating. In another embodiment it is useful when the window isunprimed.

The method of the invention allows the bonding of a window into asubstrate without the need for priming the surface of the substrateand/or the surface of the window to which it is bonded. This isespecially useful for bonding windows into automobiles.

DETAILED DESCRIPTION OF THE INVENTION

The adhesive composition of the invention contains a polymer having aflexible backbone and having silane moieties capable of silanolcondensation. The polymer with a flexible backbone can be any polymerwith a flexible backbone which can be functionalized with a silanecapable of silanol condensation. Among preferred polymer backbones arepolyethers, polyurethanes, polyolefins and the like. Among morepreferred polymer backbones are the polyethers and polyurethanes, withthe most preferred being the polyethers.

Even more preferably the polymer is a polyether having silane moietiescapable of silanol condensation. In one embodiment, the polymer usefulin the invention is a polymer as disclosed in Yukimoto et al., U.S. Pat.No. 4,906,707; Iwakiri et al., U.S. Pat. No. 5,342,914; Yukimoto U.S.Pat. No. 5,063,270; Yukimoto et al. U.S. Pat. No. 5,011,900; Suzuki etal. U.S. Pat. No. 5,650,467, all incorporated herein by reference. Morepreferably such polymers are oxyalkylene polymers containing at leastone reactive silicon group per molecule. The oxyalkylene polymer whichcan be used in the present invention includes polymers having amolecular chain represented by formula (1):

—(R—O)_(n)—  (1)

wherein R represents a divalent alkylene group having 2 to 4 carbonatoms, and preferably 2 to 3 carbon atoms; and n represents the numberof repeating units. The oxyalkylene polymer may have a straight chain ora branched structure, or a mixed structure thereof. From the viewpointof availability an oxyalkylene polymer having a repeating unitrepresented by formula (2) is preferred:

—CH(CH₃)CH₂O—  (2)

The polymer may contain other monomer units but preferably comprises themonomer unit of formula (1) in a proportion of at least about 50 percentby weight, particularly about 80 percent by weight or more. Oxyalkylenepolymers having a number average molecular weight (Mn) of about 3,000 ormore are preferred. Those having a Mn of about 3,000 to about 50,000 areeven more preferred, and about 3,000 to about 30,000, are mostpreferred. Preferably the ratio (Mw/Mn) of weight average molecularweight (Mw) to number average molecular weight (Mn) is not higher thanabout 1.6, which indicates that the polymer has an extremely narrowmolecular weight distribution (i.e., it is highly monodisperse). TheMw/Mn ratio is more preferably not higher than about 1.5, and mostpreferably not higher than about 1.4. While molecular weightdistribution is measurable by various methods, it is generally measuredby gel-permeation chromatography (GPC).

The terminology “reactive silicon group” or “reactive silane capable ofsilanol condensation” means a silicon-containing group in which ahydrolyzable group or a hydroxyl group is bonded to the silicon atom andwhich is cross-linkable through silanol condensation reaction. While notlimited thereto, typical reactive silicon groups are represented byformula (3):

wherein R¹ and R² each represent an alkyl group having 1 to 20 carbonatoms, an aryl group having 6 to 20 carbon atoms, an aralkyl grouphaving 7 to 20 carbon atoms or a triorganosiloxy group represented by(R′)₃SiO—, wherein each of the three R′ groups, which may be the same ordifferent represents a monovalent hydrocarbon group having 1 to 20carbon atoms; when there are two or more of each of the R¹ or R² groups,each of the R¹ and R² groups may be the same or different, and the R¹can be the same or different from R²; X is independently in eachoccurrence a hydroxyl group or a hydrolyzable group; when there are twoor more X groups; a is independently in each occurrence 0, 1, 2 or 3;and b is independently in each occurrence 0, 1 or 2; and m represents 0or an integer of from 1 to 19; wherein a and b are chosen to satisfy therelationship a+Σb≧1.

The hydrolyzable group represented by X is not particularly limited andis selected from conventional hydrolyzable groups. Specific examples area hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, aketoximate group, an amino group, an amido group, an acid amido group,an amino-oxy group, a mercapto group, and an alkenyloxy group. Preferredamong them are a hydrogen atom, an alkoxy group an acyloxy group, aketoximate group, an amino group, an amido group, an amino-oxygroup, amercapto group, and an alkenyloxy group. An alkoxy group, is morepreferred with a methoxy or ethoxy group being most preferred, for easein handling due to its mild hydrolyzablility. One to three hydroxylgroups or hydrolyzable groups may be bonded to one silicon atom, and(a+Σb) is preferably 1 to 5. Where two or more hydroxyl groups orhydrolyzable groups are present per reactive silicon group, they may bethe same or different. The reactive silicon group may have one or moresilicon atoms. A reactive silicon group in which silicon atoms arelinked to form siloxane bondings may have as much as 20 silicon atoms.From the standpoint of availability, reactive silicon groups representedby formula (4) shown below are preferred:

wherein R¹, X, and α are as defined above R¹ is preferably an alkylgroup, e.g., methyl or ethyl; a cycloalkyl group, e.g., cyclohexyl; anaryl group, e.g., phenyl; an aralkyl group, e.g., benzyl; or atriogansiloxy group of formula (R′)₃SiO— in which R′ is methyl orphenyl. R¹ and R′ are most preferably a methyl group.

The oxyalkylene polymer contains at least one, and preferably about 1.1to about 6 reactive silicon groups per molecule. If the number of thereactive silicon group per molecule is less than 1, the polymer hasinsufficient curability, failing to achieve satisfactory rubberyelasticity. The reactive silicon group may be placed either at theterminal or in the inside of the molecular chain of the oxyalkylenepolymer. An oxyalkylene polymer having the reactive silicon group at themolecular terminal thereof tends to provide a rubbery cured producthaving high tensile strength and high elongation.

The oxyalkylene polymer having a reactive silicon group is preferablyobtained by introducing a reactive silicon group into theabove-mentioned oxyalkylene polymer having a functional group. Processesfor the preparation of such oxyalkylene polymers are disclosed in theU.S. patents previously incorporated herein by reference. Suchoxyalkylene polymers containing at least one reactive silicone group permolecule may also be reacted with other groups or polymers reactive withsuch oxyalkylene polymer as disclosed in the above mentioned U.S.patents.

In one embodiment, the flexible polymer used in the adhesive compositionis a silyl terminated prepolymer prepared by contacting a polyol asdescribed herein with an isocyanato silane having at least one silanemoiety which has bonded thereto a hydrolyzable moiety under conditionssuch that the hydroxyl moieties of the polyol react with the isocyanatemoieties of the isocyanatosilane so as to place a terminal silane moietyon the polyol, preferably the contacting is performed without additionof catalyst.

Polyols which may be used to prepare the silyl terminated prepolymerinclude polyols useful in preparing polyurethane prepolymers useful inadhesive and elastomer applications and are well known to those skilledin the art. Bhat et al., U.S. Pat. No. 5,672,652, see column 4, lines 5to 60, (relevant parts incorporated herein by reference) discloses thepreferred polyols useful in preparing the silane terminated prepolymers.The polyols are prepared by reacting an initiator, a compound having oneor more active hydrogen atoms, with an alkylene oxide in the presence ofa suitable catalyst under appropriate conditions for the alkylene oxideto react with one or more active hydrogen moieties of the initiator soas to add a series of ether units to the initiator thereby preparing apolyol. Initiators which are useful in this invention are well-known tothose skilled in the art. Preferable initiator compounds which areemployed to prepare the polyols are compounds having 1 to 8 activehydrogens, preferably 2 to 8, more preferably 2 to 4, and mostpreferably 2 to 3 active hydrogens. Preferable initiator compoundsinclude, for example, alcohols, glycols, low molecular weight polyols,glycerine, trimethylol propane, pentaerythritol, glycosides, sugars,ethylene diamine, diethylenetriamine, and the like. Particularlysuitable glycols include, for example, ethylene glycol, 1,2-propyleneglycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol,1,4-butylene glycol, 1,2-pentylene glycol, 1,3-pentylene glycol,1,4-pentylene glycol, 1,5-pentylene glycol, 1,6-pentylene glycol,neopentyl glycol and various hexane diols, mixtures thereof and thelike. Alkylene oxides useful include ethylene oxide, propylene oxide,1,2-butylene oxide, 2,3-butylene oxide, or mixtures thereof. Mostpreferred alkylene oxides are ethylene oxide and propylene oxide, withpropylene oxide most preferred. Combinations of the above mentionedalkylene oxides may be used in random or block polymers.

Preferably, the polyols used in preparing the silane terminatedprepolymers are high molecular weight polyols prepared by the processwhich comprises first, contacting one or more initiators with one ormore alkylene oxides in the presence of a catalyst comprising calciumhaving counterions of carbonate and a C₆ to C₁₀ alkanoate in a solventwhich does not contain active hydrogen atoms. The mixture is exposed toconditions at which the alkylene oxides react with the compoundcontaining more than one active hydrogen atom. Preferably the process isperformed such that a polyol is prepared which has an equivalent weightof from about 1,000 to about 20,000, a poly dispersity of about 1.2 orless and a residual calcium level of from about 0 to about 2,000 partsper million (ppm). The preferred catalyst used in preparing the polyolsis a calcium catalyst which contains both carbonate and C₆ to C₁₀alkanoate counterions. The catalyst is dispersed or dissolved in adispersant or solvent which has no active hydrogen atoms capable ofinitiating a polyether. Preferably, the solvent or dispersant is ahydrocarbon or mixture of hydrocarbons and more preferably, mineralspirits. Preferably the alkanoate counterions are C₈ residues of organicacids. In a preferred embodiment, the alkanoates are derived fromsubstantially pure organic carboxylic acids. Preferably the purecarboxylic acids are synthetic, as synthetic carboxylic acids generallyexhibit higher purities. The carbonate counterions result from thecontacting of the calcium and the organic carboxylic acid with carbondioxide. The ratio of calcium ions to carboxylic acid ions is from about1.0:0.5 to about 1.0:1.0. Preferably the ratio is between about 1.0:0.5and about 1.0:0.9. The catalysts may be prepared by contacting theappropriate ratio of calcium hydroxide with a C₆₋₁₀ carboxylic acid andbubbling carbon dioxide through the mixture to form carbonate moieties.In the preparation of the preferred high molecular weight polyols, theinitiator and alkylene oxides are generally contacted without the use ofthe solvent. Typically such contacting takes place in the absence ofoxygen and atmospheric moisture, under an inert atmosphere, such asnitrogen or argon. The ratio of initiator to polyol is chosen to achievethe desired molecular weight or equivalent weight of the polyol. Thisratio can be readily calculated by one skilled in the art. The amount ofcatalyst used is sufficient such that the residual catalyst remaining inthe polyol upon completion of the reaction is about 0 part per millionor greater more preferably about 200 parts per million or greater, evenmore preferably about 300 parts per million or greater and mostpreferably about 400 parts per million or greater, and preferably about2,000 parts per million or less, more preferably about 1,000 parts permillion or less, even more preferably about 800 parts per million orless and most preferably about 400 parts per million or less. In someembodiments, it may be desirable to remove all of the residual catalystwhere the catalyst is not needed for a further reaction and where thecatalyst may impact the properties of the ultimate adhesive. This can beachieved by contacting the polyether polyol of the invention withmagnesium silicate or phosphoric acid and filtering the polyol withdiatomaceous earth. The complex of the calcium catalyst and theadditives are removed on the filter material. In those embodiments wherethe calcium is removed, the resulting parts per million of the catalystremaining in the polyol can be about 0.

The reactants are reacted at a temperature of about 90° C. or greater,more preferably about 100° C. or greater and most preferably about 110°C. or greater, and preferably at a temperature of about 150° C. or less,more preferably about 130° C. or less and most preferably about 120° C.or less. The reactants are contacted for a time sufficient to preparethe desired high molecular weight polyol. The reaction time iscontrolled by the feed rate, reactor size, catalyst concentration andtemperature. One skilled in the art can determine the appropriate timebased on these variables. The unreacted polyols and initiators may beremoved from the reaction by stripping them off using means well-knownto those skilled in the art.

The polyether polyol preferably has a weight average molecular weight ofabout 2,000 or greater, more preferably about 3,000 or greater, evenmore preferably about 6,000 or greater, even more preferably about10,000 or greater and most preferably 12,000 or greater. The resultingpolyether polyol preferably has a weight average molecular weight ofabout 20,000 or less, more preferably about 16,000 or less, even morepreferably about 14,000 or less and most preferably about 12,000 orless. The resulting high molecular weight polyol preferably has apolydispersity of about 1.2 or less and more preferably about 1.12 orless. Preferably the polyol used in the invention corresponds to Formula5.

R³—((CH(R⁴)CH(R⁴)O)_(q)—H)_(p)  (5)

wherein:

R³ is the residue of a compound having from about 1 to about 8 hydrogenatoms;

R⁴ is independently in each occurrence a C₁₋₆ saturated or unsaturatedhydrocarbon chain;

q is independently in each occurrence a number such that the equivalentweight of the polyol is from about 1,000 to about 20,000; and p isindependently in each occurrence from about 1 to 8. Preferably R³ is aC₁₋₈ alkyl or cycloalkyl moiety or oxygen. More preferably, R³ is a C₂to C₄ alkyl group or oxygen. R⁴ is preferably hydrogen, methyl or ethyland most preferably hydrogen or methyl. q is independently in eachoccurrence a number such that the equivalent weight of the polyol isfrom about 2,000 to about 16,000, more preferably from about 5,000 toabout 16,000 and most preferably from about 10,000 to about 14,000. p ispreferably 4 or less and more preferably 3 or less.

The polyols also demonstrate a low unsaturation level, preferably about0.04 milliequivalent of unsaturation per gram of polyol or less and morepreferably about 0.02 milliequivalent of unsaturation per gram of polyolor less.

Also included as useful polyols in this embodiment are polymers having apolyolefin backbone and terminal hydroxyl groups. Examples of suchpolyols are Kraton™ polyethylene/butylene polymers having terminalhydroxyls such as Kraton™ Liquid L-2203 polymer.

Polyalkyleneoxide based polyether polyols prepared using double metalcyanide catalysts can also be used in this invention. They areespecially attractive because of their low unsaturation level.

The polyols can be reacted with an isocyanato silane to prepare reactivesilicone functional prepolymers. Such isocyanato silane requires asilane group with a hydrolyzable moiety attached thereto. Isocyanatosilanes useful in the invention are described in U.S. Pat. No. 4,618,656at column 3, lines 24 to 34, incorporated herein by reference.Preferably such isocyanato silanes correspond to Formula 6.

wherein a, R¹ and X are as defined hereinbefore. Z is independently ineach occurrence, C₁₋₄₀ divalent hydrocarbyl moiety. Z is preferably aC₁₋₂₀ divalent hydrocarbyl moiety, preferably C₁₋₁₀ alkylpreferablyreferably C₁₋₃ alkylene and most preferably methylene.

The reaction of the polyol with an organo functional silane can beperformed using conventional processes such as those disclosed in U.S.Pat. No. 4,625,012, incorporated herein by reference. The use of thehigh molecular weight polyols described above allow the preparation ofsilane terminated polyethers by the reaction of isocyanato silanes withthe polyols without the addition of additional catalysts. The residualcalcium catalyst from the polyol formation reaction sequence describedabove is sufficient to catalyze the reaction. If desired, a standardpolyurethane catalyst such as those disclosed in U.S. Pat. No. 4,625,012at column 5, lines 14 to 23, may be added. The reaction of theisocyanato silane with a polyol can take place at a temperature of about0° C. or greater, more preferably about 25° C. or greater, andpreferably about 150° C. or less and most preferably about 80° C. orless. This reaction is preferably performed under an inert atmosphere.The reaction is allowed to proceed until the desired silanefunctionality is achieved. Where a high molecular weight polyol is usedit is preferred that a sufficient amount of isocyanato silane be used toreact with all of the hydroxyl functionality of the polyol. In thisembodiment, the resulting prepolymer exhibits excellent physicalproperties and stability. Where the polyol used is a lower molecularweight polyol, it is desirable to use less than a stoichiometric amountof isocyanatosilane as compared to hydroxyl moieties, such that theresulting product has some residual hydroxyl moieties in the prepolymerprepared. This results in a product that has better physical propertiesat cure. In this embodiment, the ratio of hydroxyl moieties toisocyanate moieties of the isocyanoto silanes is preferably from about0.75:1.0 to 0.95:1.0.

In another embodiment, the polymer may be a polyurethane based backbonehaving hydrolyzable silane groups. Such materials are disclosed inChang, U.S. Pat. No. 4,622,369 and Pohl, U.S. Pat. No. 4,645,816,relevant portions incorporated herein by reference.

In another embodiment, the backbone can be a flexible polymer such as apolyether or polyolefin, having silicon moieties having bound thereto. Aflexible polymer with unsaturation can be reacted with a compound havinga hydrogen or hydroxyl moiety bound to silicon wherein the siliconmoiety also has one or more carbon chains with unsaturation. The siliconcompound can be added to the polymer at the point of unsaturation by ahydrosilylation reaction. This reaction is described in Kawakubo, U.S.Pat. No. 4,788,254, column 12, lines 38 to 61; U.S. Pat. No. 3,971,751;U.S. Pat. No. 5,223,597; U.S. Pat. No. 4,923,927; U.S. Pat. No.5,409,995 and U.S. Pat. No. 5,567,833, incorporated herein by reference.

The polymer prepared can be cross-linked in the presence of ahydrosilylation cross-linking agent and hydrosilylation catlyst asdescribed in U.S. Pat. No. 5,567,833 at column 17, lines 31 to 57, andU.S. Pat. No. 5,409,995, incorporated herein by reference.

Selection of the polymer used in the adhesive is important to achievingshort and long term adhesion to painted substrates and ceramic frits onglass substrates without the need to prime the surface of the substrate.The preferred polymers are trialkoxysilane functional polyethers orpolyurethanes wherein the polyether or polyurethane backbone has anumber average molecular weight of about 6,000 or greater or adialkoxysilane functional polymer having a polyether or polyurethanebackbone. Preferably, the trialkoxysilane functional polymer having apolyether or polyurethane backbone has a weight average molecular weightof about 10,000 or greater and more preferably about 12,000 or greater.Preferably the polyether or polyurethane backbone has a number averagemolecular weight of 20,000 or less and most preferably 16,000 or less.

The prepolymer is present in the adhesive composition in sufficientamount such that the adhesive is capable of bonding glass to anothersubstrate, such as metal, plastic, a composite or fiberglass. Preferablythe substrates are painted and more preferably the substrates arepainted with acid resistant paints, such as acrylic melamine silanemodified coatings (DuPont Gen IV paints), melamine carbamate coatings,two part urethane coatings, or acid epoxy cure coatings. The adhesivesof the invention are especially good for bonding windows to acrylicmelamine silane modified coatings (DuPont Gen IV paints). Preferably theprepolymer is present in an amount of about 30 percent by weight orgreater based on the weight of the adhesive, more preferably about 40percent by weight or greater, even more preferably about 45 percent byweight or greater and most preferably about 50 percent by weight orgreater. More preferably the prepolymer is present in an amount of about99.8 percent by weight or less based on the weight of the adhesive andmost preferably about 85 percent by weight or less.

The adhesive composition further comprises one or more tin catalystswhich catalyzes the silanol condensation reaction. Tin catalysts usefulfor the silanol condensation reaction are well-known in the art. Theselection of the catalyst is important to achieving the desired bondingof the adhesive of the invention to a painted substrate and/or anorganic frit on glass preferably without a primer. The choice ofcatalyst is impacted by the choice of polymer. For trialkoxysilanefunctional polymers the catalyst can be a dialkyltin carboxylate(dialkyltin (IV) salts of organic carboxylates) or dialkyltinalcoholate, such as a dialkyltindialkenedione (which includes the(dialkyltinbisacetylacetonates)). For the dialkoxy functional polymersthe preferred catalysts are the dialkyltin alcoholates. Preferably thealkyl groups on the catalysts are C₁₋₄ and most preferably methyl. Thepreferred catalysts for all polymers are the dialkyltin alcoholates,with dialkyltin diacetylacetonates being most preferred. Among preferreddialkyltin carboxylates are dibutyltin diacetate, dimethyltin dilaurate,dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate and thereaction product of dialkyltin oxide and phthalic acid esters.Dialkyltin alcholates include the reaction products of dialkyltin oxidesand alkanediones, such as dialkyltin diacetyl acetonates, such asdibutyltin diacetylacetonate (also commonly referred to as dibutyltinacetylacetonate. These catalysts may be used individually or incombinations of 2 or more. Among preferred dialkyltin carboxylates areadducts of dibutyltin oxide and phthalate esters available from WitcoCorporation under the designation Fomrez SUL-11A, dimethyltindicarboxylate available from Witco Corporation under the designationFomrez UL-28, dibutyltin dilaurate available from Air Products under thedesignation T-12 and from Witco Corporation under the designation FomrezSUL-4 and dibutyltin diacetate available from Air Products under thedesignation Dabco T-1 and from Witco Corporation under the designationFomrez UL-1. The most preferred catalyst is dibutyltinbisacetylacetonate (dibutyltin dipentenedione) available from NittoKasei Co. Ltd. under the designation Neostann U-220. Catalysts whichundergo hydrolytic disassociation at a faster rate are preferred. Theamount of catalyst used in the formulation is that amount whichfacilitates the cure of the adhesive without causing degradation of theadhesive after cure and which facilitates bonding of the adhesive to thesubstrate. The preferred amount of catalyst used is dependent upon thechoice of catalyst, and the amount and selection of adhesion promoter(depending on the basicity of the adhesion promoter, among other issues.Catalysts with slower hydrolytic disassociation requires a higherconcentration to get the desired adhesion. Higher concentration ofcatalysts are preferred when the adhesion promoter has a lower basicityor concentration. The amount of catalyst in the adhesive formulation ispreferably about 0.01 percent by weight or greater, more preferablyabout 0.1 percent by weight or greater, and most preferably about 0.2percent by weight or greater, and preferably about 5 percent by weightor less, even more preferably about 1.0 percent by weight or less, evenmore preferably 0.5 percent by weight or less and most preferably about0.4 percent by weight or less.

The adhesive composition may further comprise a curing agent for thesiloxy moiety. Such compound can be a hydrolyzable silicone compound,such compounds are disclosed in U.S. Pat. No. 5,541,266, incorporatedherein by reference. Hydrolyzable silicon compounds useful include thoserepresented by formula 7:

 X_(n)—Si—R⁶ _(4-n-m)

X represents a hydrolyzable group. R⁵ represents a monovalenthydrocarbon group, and is preferably a lower alkyl group. R⁶ representsa monovalent organic group containing an amino group or an imino groupand having a ratio of carbon atom number to nitrogen atom number (C/Nratio) of more than 3. The C/N ratio is preferably 4 or more 3; mrepresents 0, 1 or 2 and preferably 0 or 1; n represents 1, 2 or 3; and(m+n) is less than 4 and preferably (m+n) is 3. n Is preferably 2 or 3.The molecular weight of the hydrolyzable silicon compound is preferably1,000 or less. R⁶ includes R⁷ N(R⁸)—R⁹—N(R¹⁰)—R¹¹ wherein R⁷ and R⁸ eachrepresents a divalent hydrocarbon group containing 2 or more carbonatoms, and at least one of R⁷ and R⁹ contains 4 or more carbon atoms.R⁸, R¹⁰, and R¹¹ each represents a hydrogen atom or a monovalenthydrocarbon group, preferably an alkyl group containing 1 to 3 carbonatoms.

The specific but non-limiting examples of the above mentionedhydrolyzable silicon compound are shown below

H₂N(CH₂)₆NH(CH₂)₃Si(OCH₃)₃,

H₂N(CH₂)₈NH(CH₂)₃Si(OCH₃)₃,

H₂N(CH₂)₆NH(CH₂)₃Si(CH₃)(OCH₃)₂,

H₂N(CH₂)₆NH(CH₂)₃Si(OCH₂CH₃)₃,

H₂N(CH₂)₂NHCH₂-ph-(CH₂)₂Si(OCH₃)₃, and

H₂N(CH₂)₄NHCH₂-ph-(CH₂)₂Si(OCH₃)₃,

wherein pH represents a p-phenylene group.

The hydrolyzable silicon compound is used in an amount of from about0.01 to about 20 parts by weight, and preferably from about 0.1 to about10 parts by weight, per 100 parts by weight of the oxyalkylene polymerhaving a reactive silicon group and capable of cross-linking on siloxanebond formation. If it exceeds about 20 parts by weight, the rubberphysical properties after curing are adversely affected.

Further examples of such hydrolyzable silicone compounds capable ofcross-linking the silicone reactive polymer are disclosed in U.S. Pat.No. 5,541,266, incorporated herein by reference. Other such potentialadditives include organic silicone compounds B as disclosed in U.S. Pat.No. 4,837,274, see columns 7, line 12 to column 9, line 15, incorporatedherein by reference.

The adhesive formulation may contain other additives commonly used inadhesives formulations as known to those skilled in the art. Theadhesive of the invention may be formulated with fillers known in theart for use in adhesive compositions. By the addition of such materials,physical properties such as viscosity, flow rates, sag and the like canbe modified. However, to prevent premature hydrolysis of the moisturesensitive groups of the prepolymer, it is preferable to thoroughly drythe fillers before admixture therewith.

Optional components of the adhesive of the invention include reinforcingfillers. Such fillers are well-known to those skilled in the art andinclude carbon black, titanium dioxide, calcium carbonate, surfacetreated silica, titanium oxide, fumed silica, and talc. Preferredreinforcing fillers comprise carbon black. In one embodiment, more thanone reinforcing filler may be used, of which one is carbon black, and asufficient amount of carbon black is used to provide the desired blackcolor to the adhesive. Preferably the only reinforcing filler used iscarbon block. The reinforcing fillers are used in sufficient amount toincrease the strength of the adhesive and to provide thixotropicproperties to the adhesive. Preferably the reinforcing filler is presentin an amount of about 1 part by weight of the adhesive composition orgreater, more preferably about 15 parts by weight or greater and mostpreferably about 20 parts by weight or greater. Preferably thereinforcing filler is present in an amount of about 40 parts by weightof the adhesive composition or less, more preferably about 35 parts byweight or less and most preferably about 33 parts by weight or less.

Among optional materials in the adhesive composition are clays.Preferred clays useful in the invention include kaolin, surface treatedkaolin, calcined kaolin, aluminum silicates and surface treatedanhydrous aluminum silicates. The clays can be used in any form whichfacilitate formulation of a pumpable adhesive. Preferably the clay is inthe form of pulverized powder, spray dried beads or finely groundparticles. Clays may be used in an amount of about 0 part by weight ofthe adhesive composition or greater, more preferably about 1 part byweight or greater and even more preferably about 6 parts by weight orgreater. Preferably the clays are used in an amount of about 20 parts byweight or less of the adhesive composition and more preferably about 10parts by weight or less.

The adhesive composition of this invention may further compriseplasticizers so as to modify the rheological properties to a desiredconsistency. Such materials are preferably free of water, inert toreactive groups and compatible with the polymer used in the adhesive.Suitable plasticizers are well-known in the art and preferableplasticizers include alkyl phthalates such as dialkyl phthalate, whereinthe alkyl phthalate is linear with mixed C₇, C₉ and C₁₁ alkyl groups,diisononyl phthalate diisododecyl phthalate, dioctylphthalate ordibutylphthalate, partially hydrogenated terpene, commercially availableas “HB-40”, trioctyl phosphate, epoxy plasticizers, toluene-sulfamide,chloroparaffins, adipic acid esters, castor oil, toluene, xylene,n-methylpyrolidinone and alkyl naphthalenes. The preferred plasticizersare the phthalates. The more preferred plasticizers are the dialkylphthalates wherein the alkyl group is mixed linear C₇, C₉ and C₁₁,diisononyl phthalate or diisododecyl phthalate. The amount ofplasticizer in the adhesive composition is that amount which gives thedesired rheological properties and which is sufficient to disperse thecatalyst and other components in the system and to give the desiredviscosity. The amounts disclosed herein include those amounts addedduring preparation of the prepolymer and during compounding of theadhesive. Preferably plasticizers are used in the adhesive compositionin an amount of about 0 part by weight or greater based on the weight ofthe adhesive composition, more preferably about 5 parts by weight orgreater, even more preferably about 10 parts by weight or greater andmost preferably about 20 parts by weight or greater. The plasticizer ispreferably used in an amount of about 45 parts by weight or less basedon the total amount of the adhesive composition, more preferably about40 parts by weight or less, even more preferably about 30 parts byweight or less and most preferably about 25 parts by weight or less.

The adhesive of this invention may further comprise stabilizers whichfunction to protect the adhesive composition from moisture, therebyinhibiting advancement and preventing premature cross-linking of thepolymer capable of cross-linking in the adhesive formulation. Includedamong such stabilizers are hydrocarbyl alkoxy silanes, such as vinyltrimethoxy silane, diethylmalonate and alkylphenol alkylates. Suchstabilizers are preferably used in an amount of about 0.1 part by weightor greater based on the total weight of the adhesive composition,preferably about 0.5 part by weight or greater and more preferably about0.8 part by weight or greater. Such stabilizers are used in an amount ofabout 5.0 parts by weight or less based on the weight of the adhesivecomposition, more preferably about 2.0 parts by weight or less and mostpreferably about 1.4 parts by weight or less.

An adhesion promoter can be added to enhance adhesion to either theglass or to the surface of the substrate to which the glass is bonded.

Selection of the adhesion promoter is important in achieving adhesion toa wide variety of paint systems and optionally ceramic frit systems onglass without the need for a primer for either the paint or the ceramicfrit. The adhesion promoters useful are primary or secondary aminostraight chain alkyl trialkoxy silanes. Preferred primary or secondaryamino straight chain alkyl trialkoxy silanes correspond to the formula

(R⁷_(x)NR⁸—SiOR⁹)₃)_(y)

wherein

R⁷ is independently in each occurrence a straight chain alkyl oraminoalkyl;

R⁸ is independently in each occurrence a straight chain alkylene group;

R⁹ is independently in each occurrence an alkyl group;

x is independently in each occurrence an integer of 0 or 1; and

y is independently in each occurrence an integer of 1 or 2;

wherein x+y is 2 or less.

Preferably R⁷ is C₁₋₆ alkyl or C₁₋₆ alkyl amino; more preferably C₁₋₃alkyl or C₁₋₃ alkylamino and most preferably ethyl amino. The aminemoiety of the alkylamine group of R⁷ is preferably located on the carbonatom furthest from the primary or secondary amine group. R⁸ ispreferably C₁₋₆, alkylene, more preferably C₂₋₄ alkylene and mostpreferably C₃ alkylene (propylene). R⁹ is preferably C₁₋₆ alkyl, mostpreferably, C₁₋₂ alkyl (methyl or ethyl) and most preferably C₁ alkyl(methyl). x is preferably 0 and y is preferably 2. Among useful adhesionpromoters are gamma-aminopropyltrimethoxy silane,n-beta-(aminoethyl)-gamma-aminopropyltrimethoxy silane,n-(2-aminoethyl)-3-aminopropylmethyldimethoxy silane,3-aminopropyl-methyldimethoxy silane,bis-(gamma-trimethoxysilyl-propyla)mine, Among more preferred adhesionpromoters are N-2-aminoethyl-3-aminopropyl trimethoxysilane (availablefrom Hills America Inc. under the tradename DAMO-P),3-aminopropyltrimethoxysilane (available from Witco Corporation underthe designation A-1110), 3-aminopropyltriethoxysilane (available fromWitco Corporation under the designation A-1100) andbis-(3-trimethoxysilylpropyl)amine (available from Witco Corporationunder the designation A-1170. The most preferred adhesion promoter isbis-(3-trimethoxysilylpropyl)amine. The amount of the adhesion promoteris chosen to be an effective amount to achieve good short term and longterm adhesion. The particular effective amount needed is dependent onthe choice of catalyst, amount of catalyst and basicity of the primaryor secondary amine in the adhesion promoter. Adhesion promoters with ahigher basicity are generally used in lower concentrations than thosewith a lower basicity. If too much or little adhesion promoter is usedpoor adhesion to the substrate may result. At higher concentrations ofthe catalyst, lower amounts of adhesion promoter are preferably used. Iftoo much total adhesion promoter and catalyst are used the adhesion tothe substrate is poor. Preferably, the adhesion promoter is used in anamount of about 0.1 percent by weight of the adhesive or greater andmore preferably 0.5 percent by weight or greater. Preferably theadhesion promoter is used in an amount of 1.2 percent by weight or lessbased on the adhesive weight and more preferably 1.0 percent by weightor less.

In addition to the adhesion promoters described above other adhesionpromoters for adhesion to coated surfaces are the amino alkoxy silanes,vinyl alkoxy silanes, isocyanto alkoxy silanes and isocyanuratefunctional alkoxy silanes. More preferred of the additional adhesionpromoters include gamma-glycidoxypropyltrimethoxy silane,gamma-isocyanatopropyltrimethoxy silane,n-phenyl-gama-aminopropyltrimethoxysilane,gamma-isocyanatopropylmethyldimethoxy silane,gamma-isocyanatopropyltriethoxy silane, beta(3,4-epoxycyclohexyl)ethyltriethoxysilane,gamma-glycidoxypropylmethyl-dirnethoxy silane,tris(gamma-trimethoxysilylpropyl)iso-cyanurate, vinyltriethoxysilane, orvinyltrimethoxysilane. Such additional adhesion promoters are present insufficient amount to promote the adhesion of the adhesive to the glassor other substrate surface to the desired level usually determined bytesting the lap shear strength and failure mode of the bond to thesubstrate. Preferably the amount of adhesion promoter is about 10 partsby weight or less based on the weight of the adhesive; more preferably 5parts by weight or less and most preferably about 2 parts by weight orless. Preferably the amount of adhesion promoter is about 0.01 part byweight or greater based on the weight of the adhesive; more preferably0.1 part by weight or greater and most preferably about 0.5 part byweight or greater.

The adhesive composition can also contain heat stabilizers known in theart. Among preferred heat stabilizers are alkyl substituted phenols,phosphites, sebacates, and cinnamates. Among more preferred heatstabilizers are bis(1,2,2,6,6,-pentamethy-4-piperidinyl) sebacate,Irgafox-168, ethylene bis(oxyethylene)bis(3-tert-butyl-4-hydroxy-5(methylhydrocinnamate), tetrakis isodecyl4,4′ isopropylidene diphosphite, and butylated hydroxytoluene. Thepreferred class of heat stabilizers are the sebactes such asbis(1,2,2,6,6,-pentamethy-4-piperidinyl) sebacate. Preferably the amountof heat stabilizer is about 5 parts by weight or less based on theweight of the adhesive; more preferably 2 parts by weight or less andmost preferably about 1.0 part by weight or less. Preferably the amountof heat stabilizer is about 0.01 part by weight or greater based on theweight of the adhesive; and most preferably about 0.5 part by weight orgreater.

Other components commonly used in adhesive compositions may be used inthe adhesive composition of this invention. Such materials arewell-known to those skilled in the art and may include ultravioletstabilizers and antioxidants.

As used herein, all parts by weight relative to the components of theadhesive composition are based on 100 total parts by weight of theadhesive composition and all percentages by weight are based on theweight of the adhesive composition. The sealant composition of thisinvention may be formulated by blending the components together usingmeans well-known in the art. Generally the components are blended in asuitable mixer. Such blending is preferably conducted in an inertatmosphere and in the absence of atmospheric moisture to preventpremature reaction. It may be advantageous to add any plasticizers tothe reaction mixture for preparing the prepolymer so that such mixturemay be easily mixed and handled. Alternatively, the plasticizers can beadded during blending of all the components. Once the sealantcomposition is formulated, it is packaged in a suitable container suchthat it is protected from atmospheric moisture. Contact with atmosphericmoisture could result in premature cross-linking of the prepolymer.

The sealant composition of the invention is used to bond porous andnonporous substrates together. The sealant composition is applied to theglass surface or the other substrate surface and is thereafter contactedwith a secondsurface of glass or substrate. Thereafter the adhesive isexposed to curing conditions. In a preferred embodiment the othersubstrate is a plastic, metal, fiberglass or composite substrate whichmay optionally be painted. This method is especially effective forsubstrates painted with an acid resistant paint. In preferredembodiments, the surfaces to which the adhesive is applied are cleanedprior to application, see for example U.S. Pat. Nos. 4,525,511;3,707,521 and 3,779,794, incorporated herein by reference. The glass isprepared by cleaning the surface to which the adhesive composition is tobe applied. A solvent wipe can be used to do this. Generally a cloth orother device with an appropriate solvent is used to clean the surface.Thereafter a primer may be applied to the portion of the window to whichthe adhesive is to be applied. Glass primers and application methods forsuch primers are well-known in the art. Typically the primer is appliedwith a brush or by a robot. A primer is not necessary where the adhesiveis formulated so as to eliminate the need for one. In a preferredembodiment of the invention, the substrate is a building or anautomobile. The adhesive is preferably deposited as a bead on theportion of the glass to be bonded into the substrate. The bead can bedeposited by any known method to those skilled in the art. In oneembodiment, the bead can be deposited using a caulking gun or similartype of manual application device. In another embodiment, the bead maybe deposited by an extrusion apparatus such as a robotic extrusionapparatus. The adhesive is located on the portion of the window whichwill be contacted with the structure into which it will be bonded. Inone preferred embodiment, the adhesive is placed about the periphery ofone face of the window. Typically the adhesive is in the form of a beadlocated about the periphery of the window. Preferably the bead is aprofiled shape along the cross-sectional plane. In the embodiment wherethe glass is window glass designed for use in automobiles, the bead isapplied to the portion of the glass to be contacted with the flange ofthe automobile window. In automobiles the adhesive bead is placed on aceramic frit coated about the edge of the window. Preferably the frit isbased on zinc, bismuth or a mixture thereof. The window can then beplaced into the structure with the adhesive contacting both the windowand the structure to which the window is to be bonded into. Thiscontacting is performed by means well-known to those skilled in the art.In particular, the glass can be placed in the structure by hand, by theuse of a robot and the like. Generally, the sealants of the inventionare applied at ambient temperature in the presence of atmosphericmoisture. Exposure to atmospheric moisture is sufficient to result incuring of the sealant. Curing may be further accelerated by applyingheat to the curing sealant by means of convection heat or microwaveheating. Preferably the sealant of the invention is formulated toprovide a working time of about 6 minutes or greater, more preferablyabout 10 minutes or greater. Preferably the working time is about 15minutes or less and more preferably about 12 minutes or less. Further,the adhesive of the invention demonstrates a cure rate after six hoursof about 50 psi (3.45 mPa) or greater, more preferably about 70 psi(4.83 mPa) or greater after six hours and more preferably about 100 psi(6.90 mPa) or greater after six hours.

Molecular weights as described herein are determined according to thefollowing procedure: determined using the Waters Model 590 GelPermeation Chromatograph. This unit is connected to a multiwave lengthdetector and a differential refractometer to measure the elution volume.A column of styrogel is used for the size exclusion and it can determinemolecular weights from 250 to 50,000. The molecular weight of theprepolymer is then determined by measuring the elution volume throughthis column using tetrahydrofuran as the eluting solvent. The molecularweight is then calculated from a calibration curve of molecular weightvs. elution volume obtained from a polystyrene polyethylene glycolcolumn. The quoted molecular weights are weight average molecularweights unless otherwise specified.

Specific Embodiments

The following examples are provided to more fully illustrate theinvention, and are not intended to limit the scope of the claim. Unlessotherwise stated, all parts and percentages are by weight.

The following are tests used for the prepared sealants.

Quick Knife Adhesion Test

A 6.3 mm (width)×6.3 mm (height)×76.2 mm (length) size sealant bead isplaced on 101.6 mm×101.6 mm piece of an acid resistant paint panel andthe assembly is cured for a specific time in the condition of 23° C. and50 percent relative humidity. The cured bead is then cut with a razorblade through to the painted surface at a 45 degree angle while pullingback the end of the bead at 180 degree angle. Notches are cut every 3 mmon the painted surface. The degree of adhesion is evaluated as adhesivefailure (AF) and/or cohesive failure (CF). In case of adhesive failure,the cured bead can be separated from the painted surface, while incohesive failure, separation occurs within the sealant bead as a resultof cutting and pulling. The tested paint substrate can be used assupplied, or treated by wiping with isopropanol (IPA) or naphtha (NP).For the sealant of the invention, adhesion of a sealant develops soonerto the treated substrate than to the untreated one.

Lap Shear Test

A sealant approximately 6.3 mm wide by 8 mm high is applied along thewidth of the glass and approximately 6 mm to 12 mm from the primed end.The paint substrate is immediately placed on the sealant and the sampleis allowed to cure at the condition of the 23° C. and 50 percentrelative humidity for 5 days. The sample was then pulled at a rate of 1inch/minute (2.5 cm/min) with an Instron Tester.

EXAMPLE 1 Preparation of a High Molecular Weight Polyether Diol

A mixture of 97.3 grams of polyglycol P1000, a 1,000 MW polypropyleneoxide diol from which essentially all of the catalyst (KOH) had beenremoved, and 9.73 g of 10 percent calcium, CEM ALL D10 (50 percent byweight calcium isooctoate in mineral spirits carrier, and which containsno glycol ether stabilizers, available from OMG Americas, Cleveland,Ohio) was placed in a dry, steam heated and stirred pressure reactorwhich was then purged with nitrogen several times. The mixture washeated to 100° C. and 1,985 grams of propylene oxide was added withrapid stirring. The product was a liquid having an equivalent weight of5,218 determined by a wet method for hydroxyl analysis. The numberaverage molecular weight of the product was 9,978, as determined by gelpermeation chromatography using polyglycol standards and apolydispersity of 1.1 determined by size exclusion chromatography (gelpermeation chromatography).

EXAMPLE 2 Preparation of High Molecular Weight Silyl TerminatedPolyether

In a dried, heated, nitrogen purged and mechanically stirred 500milliliter round bottom flask, were added 134.94 grams of the product ofExample 1, 6.33 grams of Siliquest A1310,gamma-isocyanatopropyltriethoxy-silane, and 1.52 grams dibutyl tindilaurate. The mixture was heated to 100° C. with stirring andimmediately allowed to cool to room temperature. A 30 mil. film wasdrawn on glass plates. The film was allowed to moisture cure overnight.The film was tack free in about 24 hours. The film was placed in a 70percent humidity chamber for 5 days and then placed in an oven at 50° C.overnight. The cured film had a 73 psi tensile strength, 35 psi modulus,and a 347 percent elongation at break.

EXAMPLES 3 to 7

Moisture curable sealant compositions were prepared under anhydrousconditions by compounding silylated prepolymers described below with thecomponents described below. The components, except carbon black, werecharged to a 2 gallon planetary mixer and mixed for 20 minutes undervacuum, then dried carbon black was added and mixed for 20 minutes undervacuum. Finally, the adhesive was filled into plastic tubes. Eachsealant was tested for adhesion to primed glass, primed paint, unprimedDuPont Gen IV paint, unprimed 2 part urethane paints, and unprimeddiamond coat paint using the Quick Knife adhesion test. The sealantswere also tested for tensile strength, elongation and lap shearstrength. The formulation components are compiled in Table 1. Theformulations are compiled in Table 2 and the results of testing arecompiled in Table 3.

TABLE 1 Prepolymer Kaneka S-303H methoxysilyl-terminated Apolypropyleneoxide based polyether Prepolymer Prepolymer of Example 2 BPrepolymer Kaneka SAX-400 trifunctional polypropyleneoxide C polyetherwith dimethoxymethyl silyl terminal groups having a molecular weight ofabout 20,000 Plasticizer Palatinol 711P mixed branched alkyl phthalateplasticizer Catalyst Neostann U-220 dibutyl tin bisacetylacetonateStabilizer A Silquest A-171 vinyl trimethoxy silane Adhesion SilquestA-1120 n-butyl(aminoethyl) gamma-aminopropyl Promoter A trimethoxysilaneAdhesion Silquest A-174 Gamma-methyl acryloxy propyl trimethoxy PromoterB silane Adhesion Silquest A-187 Gamma-glycidyl trimethoxypropyl silanePromoter C Heat Stabilizer B

TABLE 2 Example/Component 3 4 5 6 7 Prepolymer A 43.96 46.28 46.82Prepolymer B 49.25 Prepolymer C 55.6 Plasticizer 20.35 21.03 21.28 21.1015 Catalyst 0.44 0.46 0.47 0.45 0.40 Stabilizer A 0.76 1.71 0.70Adhesion Promoter A 1.14 1* Adhesion Promoter B 0.73 Adhesion Promoter C1.17 1.10 Carbon Black 33.38 30.30 30.66 27.40 27 Heat Stabilizer B 1*DAMO-P adhesion promoter from Hüls America, same chemical compositionas Adhesion Promoter A

TABLE 3 Example/Test   3 4 5 6 7 Quick Knife 100% Adhesion CF GlassPrimer 100% 100% CF 100% CF 100% CF CF Paint Primer 100% 100% CF 100% CF100% CF CF Gen. IV 100% 100% CF 100% CF 100% CF 100% CF CF 332 psi 2Part Paint 100% CF Diamond Coat 100% 100% CF CF 506 psi Cure Rate 1.5Hour psi 5 34 3 Hour psi 40 56 6 Hour psi 134 134 Tensile 1028 1025Strength psi Elongation 378 423 Percentage Lap Shear Mpa 2.4 3.4

EXAMPLE 8 Synthesis of Silylated Prepolymer

A polyether silylated prepolymer was prepared by thoroughly mixing2366.2 grams (0.388 eq.) of polypropylene glycol diol having hydroxylequivalent weight of 6100 with 83.8 grams (0.409 eq.) ofisocyanatopropyl trimethoxysilane. The reaction was carried out in areaction vessel at 75° C. under nitrogen blanket for about 4 hours untilno isocyanate groups could be detected by infrared analysis. 1050 Gramsof dialkyl phthalate plasticizer containing mixed C₇-, C₉- andC₁₁-linear alkyl group was added to the mixture and thoroughly mixed.The viscosity of the reaction mixture at 23° C. was 17,700 cps.

EXAMPLE 9 Synthesis of Silylated Prepolymer

A polyether silylated prepolymer was prepared by thoroughly mixing2,355.4 grams (0.438 eq.) of polypropylene glycol triol having hydroxylequivalent weight of 5,373 with 94.7 grams (0.462 eq.) ofisocyanatopropyl trimethoxysilane. The reaction was carried out in areaction vessel at 75° C. under nitrogen blanket for about 4 hours untilno isocyanate groups could be detected by infrared analysis.

1,050 Grams of the dialkyl phthalate plasticizer were added to themixture and thoroughly mixed. The viscosity of the reaction mixture at23° C. was 67,800 cps.

EXAMPLES 10-13

Polyether silylated prepolymers were prepared by reacting mixed diolscontaining polypropylene glycol diols having hydroxyl equivalent weightsof 6,100 and 1,000 with isocyanatopropyl trimethoxysilane. The reactionwas carried out in a reaction vessel by first heating to 75° C., then to85° C. under nitrogen blanket for about 4 hours until no isocyanategroups could be detected by infrared analysis. A dialkyl phthalateplasticizer was added to each mixture and thoroughly mixed. The amountsof the reactants, the plasticizer used and viscosity data are listedbelow:

TABLE 4 Example Example Example Example 10 11 12 13 Polypropylene 950900 850 800 glycol diol, ew = 6100 Polypropylene 50 100 150 200 glycoldiol, ew = 1000 Isocyanato-propyl 45.9 54.9 54.6 72.8 trimethoxy-silaneDialkyl plithalate 448 452 456 460 plasticizer Total 1493.9 1506.91510.6 1532.8 Viscosity, 23° C. 15800 14290 11600 9760 cps

EXAMPLES 14-17 Compounding of the Prepolymers

The silylated prepolymers described above were compounded with vinyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, catalyst andcarbon black. The prepolymers, vinyl trimethoxysilane,gamma-glycidoxypropyltrimethoxysilane, catalyst were charged to a 2gallon planetary mixer and mixed for 20 minutes under vacuum, then driedcarbon black was added and mixed for 20 minutes under vacuum. Finally,the adhesive was filled into plastic tubes. Compositions and physicalproperties of some adhesives prepared listed in Table 5:

TABLE 5 Example Example Example Example 14 15 16 17 Prepolymer inExample 8 1169.6 877.2 584.8 292.4 Prepolymer in Example 9 0.0 292.4584.8 877.2 Vinyl trimethoxy-silane 16.0 16.0 16.0 16.0 gamma-Glycidoxy11.2 11.2 11.2 11.2 propyltrimethoxy-silane Dibutyl tin bis(acetyl- 3.23.2 3.2 3.2 acetonate) Carbon black 400.0 400.0 400.0 400.0 Total 1600.01600.0 1600.0 1600.0 Tensile strength, psi 683 610 512 470 Elongation, %351 299 222 191 Storage modulus, 25 C 10.23 8.12 7.22 4.72 Cure rate,23° C., 50% 15.8 35.8 75.4 87.1 RH 3 hours 6 hours 43.7 69.5 137.6 140.3

EXAMPLES 18 to 57

Moisture curable sealant compositions were prepared under anhydrousconditions by compounding silylated prepolymers described below with thecomponents described below. The components, except carbon black, werecharged to a 2 gallon planetary mixer and mixed for 20 minutes undervacuum, then dried carbon black was added and mixed for 20 minutes undervacuum. Finally, the adhesive was filled into plastic tubes. Eachsealant was tested for adhesion to unprimed DuPont Gen IV paint,unprimed 2 part polyurethane paint, unprimed BASF® Ureclear paint andunprimed PPG DiamondCoat® paint using the Quick Knife Adhesion test.

The adhesives were applied to unprimed coupons coated with differentpaint compositions. The coupons were exposed to the followingconditions. All coupons were left open to the atmosphere at 23° C., 50percent relative humidity for 7 days. Some of the coupons (Condition 1)were then exposed to 100° F. (37.8° C.) at 100 percent relative humidityfor 7 days (Condition 2). Thereafter the coupons were tested accordingto the Quick Knife Adhesion test as described above. The results arecompiled below in Table 6.

Ingredients used in the adhesive formulations:

Prepolymer A Kaneka S-303H methoxysilyl-terminated polypropylene- oxidebased polyether Prepolymer C Kaneka SAX-400 trifunctionalpolypropyleneoxide polyether with dimethoxymethyl silyl terminal groupshaving a molecular weight of about 20,000 Adhesion- Promoter Adhesion- HDAMO-P N-2-aminoethyl-3- Promoter aminopropyltrimethoxysilane Adhesion-K A1110 3-Aminopropyltrimethoxysilane Promoter Adhesion- L A-11003-Aminopropyltriethoxysilane Promoter Adhesion- D A-1170Bis-(3-trimethoxysilylpropyl)amine Promoter (Y-9492) Adhesion- E Y-116393-Amino-2,2,dimethylpropyl- Promoter methyldimethoxysilane Adhesion- FY-15311 Bis-(3-trimethoxysilyl-2- Promoter methylpropyl)amine Adhesion-G  Y-9669 Phenylaminopropyltrimethoxysilane Promoter Adhesion- C  A-1873-Glycidoxypropyltrimethoxysilane Promoter Adhesion- I  Y-51873-Isocyanatopropyltrimethoxysilane Promoter Adhesion- J  A-1743-Methacryloxypropyltrimethoxy- Promoter silane Plasticizer A PalatinolN Diisononyl phthalate Plasticizer B Palatinol 711 P mixed branchedalkyl phthalate plasticizer Stabilizer A Tinuvin 765 Bis(1,2,2,6,6,-pentamethy-4- piperidinyl)sebacate Stabilizer B SilquestA-171 Vinyltrimethoxy silane Filler CSX-316 Carbon black

TABLE 6 Example 18 19 20 21 22 23 24 25 26 27 28 29 30 31 Polymer C C CC C C C C C C C C C C Polymer Amount 56.1 56.3 56.4 56.6 56.5 56.8 55.856.3 56.4 55.8 56.3 56.5 56.1 55.8 Plasticizer A A A A A A A A A A A A AA Plasticizer amount 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.015.0 15.0 15.0 15.0 Adhesion promoter AP H H H H H H K K K L L L D D APamount 0.5 0.5 0.5 0.25 0.5 0.25 1.0 0.5 0.25 1.0 0.5 0.25 0.5 1.0Catalyst Amount 0.4 0.25 0.1 0.1 0 0 0.25 0.25 0.25 0.25 0.25 0.25 0.40.25 Stabilizer A A A A A A A A A A A A A A Stabilizer Amount 1.0 1.01.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Carbon Black amount 27.027.0 27.0 27.0 27.0 27.0 27.0 27.0 27.0 27.0 27.0 27.0 27.0 27.0 ResultsGen IV Cond 1 CF CF CF CF AF AF CF Gen IV Cond 2 CF CF CF DC Cond 1 AFCF CF AF AF AF CF CF AF CF G G AF CF DC Cond 2 AF CF 80AF CF AF CF AF CFUC Cond 1 AF AF CF AF AF AF CF CF AF CF G G AF CF UC Cond 2 AF CF CF CFAF CF AF CF 2K Cond 1 CF CF 2K Cond 2 CF CF Example 32 33 34 35 36 37 3839 40 41 42 43 44 45 Polymer C C C C C C C C C C C C C C Polymer Amount56.3 56.3 56.6 56.4 55.8 56.3 56.5 55.8 56.3 56.5 56.1 55.8 56.3 56.5Plasticizer A A A A A A A A A A A A A A Plasticizer amount 15.0 15.015.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 Adhesion promoterAP D D D D E E E F F F G G G G AP amount 0.5 0.5 0.25 0.5 1.0 0.25 0.251.0 0.5 0.25 0.5 1.0 0.5 0.25 Catalyst Amount 0.25 0.25 0.25 0.1 0.250.25 0.25 0.25 0.25 0.25 0.4 0.25 0.25 0.25 Stabilizer A A A A A A A A AA A A A A Stabilizer Amount 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.01.0 1.0 1.0 Carbon Black amount 27.0 27.0 27.0 27.0 27.0 27.0 27 27 2727 27 27 27 27 Results Gen IV Cond 1 CF CF CF Gen IV Cond 2 CF DC Cond 1AF AF AF AF CF AF G 60CF AF AF AF AF AF AF DC Cond 2 CF AF CF AF CF AFAF AF AF AF AF UC Cond 1 AF AF AF AF AF AF G AF AF AF AF AF AF AF UCCond 2 AF AF AF AF AF AF AF AF AF AF AF 2K Cond 1 CF 2K Cond 2 CFExample 46 47 48 49 50 51 52 53 54 55 56 57 Polymer C C C C C C C C C AA A Polymer Amount 55.8 56.3 56.5 55.6 55.6 55.6 55.8 56.3 56.5 46.846.3 46.3 Plasticizer A A A A A A A A A B B B Plasticizer amount 15.015.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 21.3 21.0 21.0 Adhesion promoterAP C C C I I I J J J C I AP amount 1.0 0.5 0.25 1.0 0.5 0.25 1.0 0.50.25 0 1.18 1.18 Catalyst Amount 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.250.25 0.46 0.46 0.46 Stabilizer A A A A A A A A A B B B Stabilizer Amount1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.77 0.75 0.75 Carbon Black amount27 27 27 27 27 27 27 27 27 30.7 30.7 30.7 Results Gen IV Cond 1 CF CF CFGen IV Cond 2 DC Cond 1 AF AF AF AF AF AF AF AF AF AF AF CF DC Cond2 AFAF AF AF AF AF AF AF AF UC Cond 1 AF AF AF AF AF AF AF AF AF UC Cond 2AF AF AF AF AF AF AF AF AF 2K Cond 1 AF AF AF 2K Cond 2 G means gelled.

The tested paint systems present different levels of difficulty withrespect to the ability of an adhesive to bond to the paints withoutusing a primer. The difficulty level relative to bonding to the paintswithout the use of a primer are listed in the order of increasingdifficulty to bond to, DuPont Gen IV paints, 2 part polyurethane paints,PPG Diamond Coat paint and BASF Ureclear paint.

Examples 18 to 57 show that adhesives containingaminopropylalkoxysilanes bond to more paint systems without requiringthe use of a primer to prepare the surface than other known adhesionpromoters. Adhesives containing other adhesion promoters do not reliablybond to Diamond Coat paint, Ureclear paint or 2 part polyurethane paintswithout a primer.

Example 18 shows that Adhesion Promoter H demonstrates adhesion toDuPont Gen IV paint and to 2 part polyurethane paint. Examples 22 and 23show that an adhesive without organotin catalyst has no adhesion.Example 25 shows that Adhesion Promoter K, A-1110,3-aminopropyltrimethoxysilane, bonds to unprimed PPG Diamond Coat® paintand unprimed DuPont's Uraclear® paint. Examples 24 to 26 show the impactof catalyst and adhesion promoter concentration on adhesion. Based onthis data it is expected that an adhesive containing Adhesion Promoter Kwould bond to unprimed DuPont Gen IV paint and 2 part polyurethanecoated substrates.

Example 27 shows that adhesives containing Adhesion Promoter L, A11003-aminopropyltriethoxysilane bonds to unprimed PPG Diamond Coat paintand to unprimed BASF Ureclear paint coated substrates. Based on thisdata it is expected that an adhesive containing Adhesion Promoter Lwould bond to DuPont Gen IV and 2 part polyurethane paint coatedsubstrates. Example 30 shows that an adhesive containing AdhesionPromoter D, Y9492 bis (3-trimethoxysilylpropyl) amine bonds to DuPontGen IV paint and 2 part polyurethane paint coated substrates. Example 31shows that an adhesive containing Adhesion Promoter D bonds to BASFUreclear paint and PPG Diamond Coat paint coated substrates.

Examples 6 to 48 and 55 show that an adhesive containing AdhesionPromoter H, 3-glycidyloxypropyl-trimethoxysilane, bonds to unprimedDuPont Gen IV paint. The adhesive does not bond to PPG Diamond Coatpaint, BASF Ureclear and 2 part polyurethane paint coated substrates.

Examples 49 to 51 demonstrate that an adhesive containing adhesionPromoter I, Y5187, 3-isocyanatopropyltrimethoxysilane, does not bond toPPG Diamond Coat paint and to BASF Ureclear paint coated substrates.Example 57 shows a different adhesive composition using adhesionpromoter I bonding to DuPont Gen IV paint and PPG Diamond Coat paintcoated substrates but not to unprimed 2 part polyurethane paint coatedsubstrates. Examples 52 to 54 demonstrate that Adhesion Promoter J doesnot bond to PPG Diamond Coat paint and BASF Ureclear coated substrates.

EXAMPLES 58 to 69

Two series of several adhesives were prepared and tested on threeunprimed coated surfaces. One series used dimethoxy silyl polymers(Prepolymer A) formulated as described above using the formulationsdescribed below.

In a second series the polymer was a trimethoxy functional silaneprepared as described in Example 2. The adhesive was formulated asdescribed above using the components listed in Table 7 below.

TABLE 7 IngredientsExample 58 60 62 64 66 68 Prepolymer A 44.0 44.0 44.044.0 44.0 44.0 Plasticizer B 20.2 20.2 20.2 20.2 20.2 20.2 AdhesionPromoter H 1.14 1.14 1.14 1.14 1.14 1.14 Adh Promoter J 0.73 0.73 0.730.73 0.73d 0.73 Filler 33.5 33.5 33.5 33.5 33.5 33.5 SUL-11A 0.45 T-10.45 UL-28 0.45 UL-29 0.45 U-220 0.45 T-12 0.45 Total 100.00 100.0 100.0100.0 100.0 100.0 Ingredients/Example 59 61 63 65 67 69 Trimethoxysilane44.0 44.0 44.0 44.0 44.0 44.0 Plasticizer B 20.2 20.2 20.2 20.2 20.220.2 Adhesion Promoter H 1.14 1.14 1.14 1.14 1.14 1.14 Adh Promoter J0.73 0.73 0.73 0.73 0.73d 0.73 Filler 33.5 33.5 33.5 33.5 33.5 33.5SUL-11A 0.45 T-1 0.45 UL-28 0.45 UL-29 0.45 U-220 0.45 T-12 0.45 Total100.00 100.0 100.0 100.0 100.0 100.0

The adhesive bond to Dupont Gen IV, coating a 2 part polyurethanecoating (2K) and BASF Ureclear Coating were tested according to theQuick Knife Adhesion tests. Several tin catalysts were used in theseries, Fomrez SU-11A catalyst, which is the reaction product ofdibutyltin oxide and phthalate ester; Dabco T-1 dibutyltin diacetate;Fomrez UL1-28 dimethyltin dicarboxylate; (Catalyst B) Fomrez UL-29dimethyltin dimercaptide, Dabco T-12 dibutyltin dilaurate (Catalyst C)and U-220 dibutyltin deacelylacetonate (Catalyst A). The results arecompiled in Table 8.

TABLE 8 Example Functional Group Catalyst Results¹ 58 DimethoxysilaneSU-11A CF GenIV 59 Trimethoxysilane SU-11A CF GenIV, 2K 60Dimethoxysilane  T-1 Did not cure² 61 Trimethoxysilanes  T-1 CF Gen IV,2K 62 Dimethoxysilane UL-28 Did not cure² 63 Trimethoxysilane UL-28 CFGenIV, 2K 64 Dimethoxysilane UL-29 Did not cure 65 TrimethoxysilaneUL-29 Did not cure 66 Dimethoxysilane U-220 CF GenIV, 2K, Ureclear 67Trimethoxysilane U-220 CF GenIV, 2K, Ureclear 68 Dimethoxysilane T-12Did not cure² 69 Trimethoxysilanes T-12 CFGenIV, 2K ¹CF means adhesivefailure when bonded to the listed surface. If not listed the adhesivedemonstrated adhesive failure on the surface tested. ²The adhesive didnot cure.

EXAMPLES 70-120

Several adhesive formulations were prepared as described hereinbefore,using the components described in Table 9, prepolymer D is adimethoxysilyl functional difunctional polypropyleneoxide basedpolyether having a molecular weight of about 20000 available fromKaneka. Prepolymer E is a trimethoxysilyl functional polyurethaneprepolymer prepared from 4000 a Mw polypropylene oxide based polyethermethyl diphenyl isocyanate and phenylaminopropyl trimethoxysilane, inthe ratio of 2:3:2. The prepolymer was prepared according to Example 2.In the formulations prepared 15 parts of Plasticizer A, 1.0 part ofstabilizer A (except for Examples 88, 89, 93 and 94 which used 0.5 partsof Stabilizer A and 0.8 parts of Tinurvin 213 substituted benzotriazole13 percent in polyalkylene glycol) and 27 parts of CSX-316 carbon blackfiller. The total parts were 100 parts. The adhesives were applied toglass plates having three different ceramic frit coatings. Ceramic fritcoating 1 is a bismuth zinc based enamel, gravity bend. Ceramic fritcoating 2 is zinc based enamel. Ceramic frit coating 3 is a bismuth zincenamel. Samples were exposed to various conditions before testing. InCondition 3 samples were exposed to 100° F. at 100 percent relativehumidity for 14 days. In Condition 4 samples were exposed to 90° C. at23 percent relative humidity for 14 days. In Condition 5 samples wereimmersed in water at 32° C. for 10 days. In Condition 6 samples wereexposed for 2000 hours in a Weatherometer (WOM). In Condition 7 sampleswere exposed for 2500 hours in a WOM. The WOM was operated according toSAE J1895 conditions. The samples were exposed continuously to thefollowing cycles; 89° C. at 5 percent RH for 3.8 hours and 95 percent RHfor 1 hour. The samples exposed to the WOM were tested according to theQuick Knife Adhesion and Lap shear tests described above. The resultsare compiled in Table 9.

TABLE 9 Prepolymer 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84Prepolymer 56.1 56.4 56.6 56.5 56.8 55.8 56.3 56.5 55.8 56.3 56.5 55.856.3 56.5 55.75 parts Adhesion C C C C C L L L E E E K K K D Promoter APAmount 0.5 0.5 0.25 0.5 0.25 — — — — 0.5 0.25 1.0 0.5 0.25 0.25 Cat A AA — — A A A A A A A A A A Cat Amount 0.4 0.1 0.1 — — 0.25 0.25 0.25 0.250.25 0.25 0.25 0.25 0.25 1.0 Frit 1 Cond 1 — — — — — CF gelled gelled AFAF gelled CF CF CF CF Cond 3 — — — — — AF — — AF AF — 50AF 40AF CF CFCond 4 — — — — — — — — — — — — — — CF Cond 5 — — — — — — — — — — — — — —CF Cond 6 — — — — — — — — — 351.3/100CF Cond 7 — — — — — — — — —440.5/100CF Frit 2 Cond 1 — — — — — — — — — — — — — — CF Cond 3 — — — —— — — — — — — — — — CF Cond 4 — — — — — — — — — — — — — — CF Cond 5 — —— — — — — — — — — — — — 30-40CF Cond 6 — — — — — — — — — — — — — —550/100CF Cond 7 — — — — — — — — — — — — — — 330.6/100AF Frit 3 Cond 1CF CF CF AF AF — — — — — — — — — CF Cond 2 CF/AF AF — — — — — — — — — —— — CF Cond 4 CF CF — — — — — — — — — — — — CF Cond 5 — — — — — — — — —— — — — — CF Cond 6 CF AF — — — — — — — — — — — — 466/100CF Cond 7 — — —— — — — — — — — — — — 210/100AF Prepolymer 85 86 87 88 89 90 91 92 93 9495 96 Prepolymer 56.25 56.00 55.50 55.3 27.7 56.1 56.1 28.1 55.8 28.055.8 56.3 parts Adhesion D D D D A/D D D D A/D D D D Promoter AP Amount0.25 0.5 1.0 1.0 1.0 0.5 0.5 0.5 0.5 0.5 1.0 0.5 Cat A A A A A A A A A AA A Cat Amount 0.5 0.5 0.5 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.25 0.25 Frit 1Cond 1 CF CF CF CF CF — — — — — CF CF Cond 3 CF CF CF CF CF — — — — — CFCF Cond 4 CF CF CF CF CF — — — — — CF CF Cond 5 CF CF 95-100CF CF CF — —— — — CF CF Cond 6 436.6/100CF 493.7/100CF 443.4/100CF AF AF — — — AF AF439.3/100CF 457.9/100CF Cond 7 455.9/33CF 501.3/80CF2 416.8/40CF — — —476.0/100AF 512.8/100A 67AF 0AF 60AF Frit 2 — Cond 1 CF 95-100CF CF AFAF — — — — — CF CF Cond 3 CF CF CF — — — — — — — 90CF CF Cond 4 CF CF CF— — — — — — — 95-100CF CF Cond 5 CF CF CF — — — — — — — CF CF Cond 6545/100CF 497/100CF 561/100CF — — — — — — — 418/100CF 441/100CF Cond 7293.1/100AF 596.2/100AF 459/100AF — — — — — — — 289.5/100AF 498.5/100AFFrit 3 Cond 1 CF 80-90CF 95-100CF — — CF CF CF — — CF 80-100CF Cond 2 CFCF CF — — CF CF CF — — CF CF Cond 4 CF CF 80-100CF — — CF CF CF — — CFCF Cond 5 CF CF 95CF — — — — — — — CF AF Cond 6 606.9/100 461.8/33CF6482.4/77CF — — — — — — — 326.9/60C4 404.4/67CF3 CF 7AF 23AF 0AF 3AF Cond7 352.8/100AF 379.1/100AF 356.9/100AF — — CF/AF AF CF — — 253.5/100AF229.9/100AF Prepolymer 97 98 99 100 101 102 103 104 105 106 107 108 109110 111 112 Prepolymer 56.3 56.6 56.4 55.8 56.3 56.5 55.6 56.1 55.8 56.356.5 55.8 56.3 56.5 55.6 55.6 parts Adhesion D D D F F F G G G G G C C CC I Promoter AP Amount 0.5 0.25 0.5 1.0 0.5 0.25 1.0 0.5 1.0 0.5 0.251.0 0.5 0.25 1.0 0.5 Cat A A A A A A A A A A A A A A A A Cat Amount 0.250.25 0.1 0.25 0.25 0.25 0.4 0.4 0.25 0.25 0.25 0.25 0.25 0.25 0.4 0.25Frit 1 Cond 1 — CF — CF 60CF 80CF — — AF AF AF AF AF AF — 90CF Cond 3 —CF — CF CF CF — — AF AF AF AF AF AF — CF Cond 4 — CF — — — — — — — — — —— — — — Cond 5 — CF — — — — — — — — — — — — — — Cond 6 — 429.3/100CF — —— — — — — — — — — — — — Cond 7 — 334.6/100AF — — — — — — — — — — — —Frit 2 — — — — — — — — — — — Cond 1 — CF — — — — — — — — — — — — — —Cond 3 — CF — — — — — — — — — — — — — — Cond 4 — CF — — — — — — — — — —— — — — Cond 5 — CF — — — — — — — — — — — — — — Cond 6 — 500/100CF — — —— — — — — — — — — — — Cond 7 — 214.7/100AF — — — — — — — — — — — — — —Frit 3 Cond 1 — CF — — — — — — — — — — — — — — Cond 2 — 90-100CF — — — —— — — — — — — — — — Cond 4 — CF — — — — — — — — — — — — — — Cond 5 —AF/CF mix — — — — — — — — — — — — — — Cond 6 — 494.4/100CF — — — — — — —— — — — — — — Cond 7 — 323.2/100AF — — — — — — — — — — — — — —Prepolymer 113 114 115 116 117 118 119 120 Prepolymer 55.6 55.6 55.856.3 56.5 55.8 55.8 55.8 parts Adhesion C C B B B D D D Promoter APAmount 0.25 1.0 1.0 0.5 0.25 1.0 1.0 1.0 Cat A A A A A A C B Cat Amount0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Frit 1 Cond 1 AF AF AF AF AF CF20CF AF Cond 3 AF AF AF AF AF 10CF AF AF Cond 4 — — — — — AF AF AF Cond5 — — — — — AF AF 40-50AF Cond 6 — — — — — AF AF AF Cond 7 — — — AF AFAF Frit 2 — — — — — AF AF AF Cond 1 — — — — — AF AF AF Cond 3 — — — — —50-60CF 40-50CF 40-50AF Cond 4 — — — — — 10CF AF AF Cond 5 — — — — — AFAF AF Cond 6 — — — — — 70-80CF AF AF

What is claimed is:
 1. An adhesive composition comprising a) i) atrialkoxysilane functional polyether or polyurethane wherein thepolyether or polyurethane has a weight average molecular weight of 6000or greater and a dialkyltin carboxy late or dialkyltin alcoholate; orii) a dialkoxysilane functional polyether or polyurethane and adialkyltin alcoholate; and b) a secondary amino straight chain alkyltrialkoxysilane; wherein the dialkyltin carboxylate or dialkyltinalcoholate is present in an effective amount to facilitate bonding ofthe adhesive to a substrate of from about 0.1 to about 1.0 percent byweight based on the weight of the adhesive and the secondary aminostraight chained alkyl trialkoxysilane is present in an amount which iseffective to facilitate bonding of the adhesive to a substrate whereinthe amount is from about 0.5 to about 1.2 percent by weight.
 2. Thecomposition according to claim 1 wherein the amino alkyl trialkoxysilanecorresponds to the formula (R⁷_(x)NR⁸—SiOR⁹)₃)_(y) wherein R⁷ isindependently in each occurrence a straight chain alkyl; R⁸ isindependently in each occurrence a straight chain alkylene group; R⁹ isindependently in each occurrence an alkyl group; x is independently ineach occurrence an integer of 0 or 1; and y is an integer of 1 or 2;wherein x+y is
 2. 3. The adhesive of claim 2 wherein R⁷ is independentlyin each occurrence C₁₋₆ alkyl; R⁸ is independently in each occurrenceC₁₋₆ alkylene; and R⁹ is independently in each occurrence C₁₋₆ alkyl. 4.The adhesive of claim 3 wherein R⁷ is independently in each occurrenceC₁₋₃ alkyl; R⁸ is independently in each occurrence C₂₋₄ alkylene; and R⁹is C₁₋₂ alkyl.
 5. The adhesive of claim 3 wherein the R⁸ is propylene;and R⁹ is methyl.
 6. The adhesive of claim 5 wherein x is 0 and y is 2.7. The adhesive of claim 2 wherein the catalyst is a dialkyltinalcoholate.
 8. The adhesive of claim 7 wherein the catalyst is presentin an amount of from about 0.1 to about 0.5 percent by weight.
 9. Theadhesive of claim 8 wherein the catalyst is a dialkyltin bisacetylacetonate.
 10. An adhesive composition comprising a) i) atrialkoxysilane functional polyether or polyurethane wherein thepolyether or polyurethane backbone has a weight average molecular weightof 10,000 or greater and a dialkyltin carboxylate or dialkyltinalcoholate; or ii) a dialkoxysilane functional polyether or polyurethaneand a dialkyltin alcoholate; and b) a primary or secondary aminostraight chain alkyl trialkoxysilane; wherein the dialkyltin carboxylateor dialkyltin alcoholate is present in an effective amount to facilitatebonding of the adhesive to a substrate of from about 0.1 to about 1.0percent by weight based on the weight of the adhesive and the primary orsecondary amino straight chained alkyl trialkoxysilane is present in anamount which is effective to facilitate bonding of the adhesive to asubstrate wherein the amount is from about 0.5 to about 1.2 percent byweight.
 11. The composition according to claim 10 wherein the aminoalkyl trialkoxysilane corresponds to the formula(R⁷_(x)NR⁸—SiOR⁹)₃)_(y) wherein R⁷ is independently in eachoccurrence a straight chain alkyl or aminoalkyl; R⁸ is independently ineach occurrence a straight chain alkylene group; R⁹ is independently ineach occurrence an alkyl group; x is independently in each occurrence aninteger of 0 or 1; and y is an integer of 1 or
 2. 12. The adhesive ofclaim 11 wherein R⁷ is independently in each occurrence C₁₋₆ alkyl orC₁₋₆ alkylamino; R⁸ is independently in each occurrence C₁₋₆ alkylene;and R⁹ is independently in each occurrence C₁₋₆ alkyl.
 13. The adhesiveof claim 12 wherein R⁷ is independently in each occurrence C₁₋₃ alkyl orC₁₋₃ alkylamino; R⁸ is independently in each occurrence C₂₋₄ alkylene;and R⁹ is C₁₋₂ alkyl.
 14. The adhesive of claim 12 wherein the R⁷ isethylamino; R⁸ is propylene; and R⁹ is methyl.
 15. The adhesive of claim14 wherein x is 0 and y is
 2. 16. The adhesive of claim 11 wherein thecatalyst is a dialkyltin alcoholate.
 17. The adhesive of claim 16wherein the catalyst is present in an amount of from about 0.1 to about0.5 percent by weight.
 18. The adhesive of claim 17 wherein the catalystis a dialkyltin bis acetylacetonate.